New valuable vat dyestuffs of the anthraquinone series



Patented Nov. 11, 1930 UNITED STATES PATENT OFFIC WALTER MIEG, OF O'I'LAIDE'N, GERMANY, ASSIGNOR TO GENERAL ANILINE WORKS, INC.,

' OF NEW YORK, N. Y., A CORPORATION OF DELAWARE NEW VALUABLE VAT DYESTUFFS OF THE ANTHRAQUINONE SERIES No Drawing.

The present invention relates to new valuable vat dyestuffs of the anthraquinone series, and more particularly to products having most probably the following general formula:

, l ll l V wherein at stands for hydrogen or halogen but at least one a0 being a halogen atom and y stands for hydrogen or an acylamino group, but at least one 3 being an acylamino group. 'llhese dyestuffs are prepared by acting with a condensing agent of an acid character such as concentrated sulfuric acid, chlorosulfonic acid and a mixture of 35 parts of aluminium chloride and 1 part of sodium chloride or 325 parts of pyridine on a dianthraquinonylamine containing an acridone rlng which is substituted by at least one halogen atom and containing at least one acylainino group. The condensation is carried out at a temperature of about 10l0 C. and higher when the condensation is effected by means of sulfuric acid or chlorosulfonic acid and at 130160 G. and higher when a mixture of aluminium chloride and sodium chloride or pyridine is used as condensing agent. The quantity of the condensing agent employed may vary within wide limits; I prefer to use about ten times the quantity of the starting material, when sulfuric acid and chlorosultonic acid are used as condensing agents and three to five times the quantity when aluminiumchloride-sodium chloride or aluminiumchloride pyridine is used.

The condensing action proceeds in two stages, firstly on intermediate product is formed, whose nature is up to now unknown Application filed July 8, 1929, Serial No. 376,862, and in Germany Ju1y'9, 1828.

and this intermediate product is then oxidized to the vat dyestuff. \Vhen effecting the condensation with chlorosulfonic acid at normal temperature or with strong sulfuric acid at an elevated temperature say about 4.0 C. the oxidation of the first formed condensation product proceeds in the same process; when working with a mixture of aluminiumchloride and sodiumchloride or pyridine or with sulfuric acid at normal temperature say about l020'C. it is necessary to oxidize the obtained condensation product by means of sodium nitrite, air, sodium hypochlorite.

The products obtainable in this manner by carbazole ring formation are valuable vat dyestuffs. They dye cotton in the vat from reddish-grey to olive-brown shades with excellent fastness properties. In the dry state they are dark powders dissolving in concentrated sulfuric acid with an intense coloration and being readily vatted by an alkaline hydrosulfite solution.

vThe invention is illustrated by the following examples, without being limited there to; the parts being by weight.

Example 1.-1() parts of the dianthraquinonylamine derivate obtained by the condensation of one molecular proportion of trichloroanthraquinone acridone (German Pat. No. 258,561, Example l) with one molecular proportion of 1-benZolyan1ino-5-- amino-anthraquinone are dissolved in 100 parts of concentrated sulfuric acid. The solution, which is at first yellowish-brown, quickly acquires, even at the ordinary temperature a brownish-olive coloration. On stirring into water there is produced a dark green precipitate, whichon the addition of suitable oxidizing agents, such as sodium nitrite or a sodium hypochlorite solution, becomes a dark olive-brown. vAfter then heating to about 7 0 C. a dyestulf is obtained, which dissolves in concentrated sulfuric acid with a deep blue coloration and dyes cot-ton fast blackish-ln'own shades, while therstarting material, vatted as a powder, yields greenish-grey dyeings.

Ewample Q.One molecular proportion of the amino compound obtainable by reduction of the nitrated chloroanthraquinone acridone (U. S. Pat. Ser. No. 1,052,507, Ex-

ample 1) is condensed to the dianthraquinonylamine derivative with one molecular proportion of 1-benzoyl-an1ino-5-chloro-anthraquinone in the customary manner by heating in a high boilingsolvent in the presence of anhydrous sodium acetate and small quantities 'of a" copper salt. To convert the dianthraquinonylamine derivatives into the carbazole it is stirred at room temperature into parts of chlorosulfonic acid. A deep blue solution is very soon formed, from when the closing of the carbazole' ring is which on pouring into water a dark olivebrown precipitate is produced. The dyestufi thus obtained is identical with that of Example 1. Ithasthe following probable formula OqH5.CO-NH o v v The same vat'dyestufi is also obtained carried out with other acid condensing. agents, for example by means of an aluminium chloride melt.

I claim:

1. Asnew products the compounds of the probable general formula:

substituted by halogen and one y stands for an acylamino groupand the other ys for hydrogen atoms which may) be substituted by acylamino groups, being in the dry state dark powders dissolving in concentrated sulfuric acid with an intense col oration and dyeing cotton from an alkaline hydrosulfite vat reddish-grey to olive-brown shades of excellent fastness properties.

2. As a new product the compound of the o CaH5.COI lH l being in the dry stage a black-brown powder dissolving in concentrated sulfuric. acid.

with a deep blue coloration, yielding readily with an alkaline hydrosulfite solution a yel-' low-brown vat and dyeing cotton therefrom 7 in black-brown shades of excellent fastness properties.

I In testimony whereof I have hereunto set my hand.

lVALTER MIEG.

wherein one x jstands forfhalogen the 7 other ws-for hydrogenatoms which may be r 

